Method of making colored textile yarns and fabrics



Patented June 2, 1936 attain parent entice METHOD OF MAKING CUILORED TEXTEE YARNS AND FABRICS William Whitehead, Gumberland, Md, assignor to Celanese Corporation of America, a corporation of Delaware No Drawing. Application March 2, 1934,

- Serial No. 713,783

'7 Claims.

This invention relates to the production of textile yarns and fabrics having color imparted thereto and to the colored textile yarns and fabrics.

An object of the invention is the application of a dye" or coloring material from a liquid medium to a yarn or fabric by such a method that substantially all the dye or coloring material is used from the liquid medium to impart color to the yarn or fabric.

Another object of the invention is the imparting of a deeper color or a more even color to a given quantity of textile material for the same amount of coloring material than heretofore possible. Other objects of the invention will be apparent from the following detailed description.

This invention is especially adapted to the dyeing or imparting of color to yarns and fabrics containing organic derivatives of cellulose such as the organic esters or ethers of cellulose. Exw amples of organic esters of cellulose are cellulose acetate, cellulose formate, cellulose propionate and cellulose butyrate, while examples of organic ethers of cellulose are ethyl cellulose, methyl cellulose and benzyl cellulose.

In the dyeing of such materials prior to this invention, the dyestuffs that have been used principally, and that have given the best light fastness and scour fastness, were not soluble in water or only very slightly so, therefore, they could not be applied to yarn or fabric from solution in an aqueous dye bath. Accordingly, the principal method of dyeing has been to dye from an aqueous bath having dispersed therein fine particles of a dye having an affinity for the material being dyed. It has been impossible, however, to keep the dye in fine particle form and evenly dispersed even with the aid of carriers, such as Turkey red oil, as the dyes have a tendency to recrystallize or physically unite upon two or more particles contacting with each other. Also the bath -rapidly settles out if not vigorously agitated.

According to this invention, the dye material is maintained in a finely divided state and evenly distributed throughout the aqueous dye bath. The dye material is dissolved in a carrier and the carrier is then emulsified in the bath, the carrier forming a somewhat permanent emulsion with the water. up the dissolved dye to the yarn or fabric to the extent of above 99% of the dye in the bath. The carrier in the emulsion will, moreover, pick up excessive or added dye particles as its original The emulsion, however, readily yields supply is used and in turn deliver it to the yarn and fabric.

In dyeing from dispersions of dyestuffs, the yarns and fabrics show a selection for the finer particles of dyestuif leaving the larger particles 5 to settle in the dye bath or recrystallize into still larger particles. By this invention recrystallization of the dyestuff in the bath is inhibited and the dyestuff remains in such a finely divided state that it will be exhausted from the bath. Further, when using a dye prepared according to this invention in a paste for printing purposes there are no large particles formed that will produce spots of concentrated color known in the trade as a specky condition. This specky condition is also prevented in dyeing in a dye bath when dyeing fabrics on the jig or on the winch.

Yarns and fabrics that have been treated with oil or oily coatings, according to this invention, need not be sourced prior to dyeing as is customary in other dyeing operations employing an aqueous bath. By this invention yarns and fabrics are given a level dyeing even though they have been pretreated with mineral oil and/or vegetable oils. The solvent emulsifier for the dye is also an emulsifier for the oily coating and therefore by increasing the amount of emulsifying agent the oily coating may be scoured from the yarns at the same time that they are dyed.

The dye particles being maintained in solution in a medium and in a state of division most favorable to dyeing operations, the color imparted to the yarn or fabric is not only level but of a: much richer and deeper shade. There is imparted to the dye material the property of rapidly and thoroughly penetrating into the yarn and fabric thus dyeing to the same extent the warp and weft of fabrics and the inner and outer filaments of yarn whether the yarn has a high twist or not. The invention therefore lends itself especially 40 well to the dyeing of closely woven lining twills, highly twisted crepes and like fabrics. Due to the high penetration power of the dye in the dissolved form, it may also be applied to films and foils. The invention also lends itself especially well to the dyeing of yarn in the package, such as dyeing of cheeses, cops, cones, warps and the like in processes where the dye liquor is pumped through or induced to flow through the windings on the package by means of force pumps, vacuum or other means.

This invention has the particular advantage over prior methods of dyeing in that it greatly reduces the time the material must remain in the dye bath. Yarns and fabrics take on as deep and level a color in from 2 to 10 minutes when treated according to this invention as they would in from 30 to 60 minutes by the prior methods. This factor makes for a great; saving in time, labor and amount of equipment necessary to dye a given quantity of material. This factor is also of importance for the reason that the yarns or fabrics are not in a wetted condition for any great length of time, thereby avoiding the dangers of stretching the filaments, changing the lustre, reducing the strength of the filaments and other hazards which accompany the wetting of yarns and fabrics, especially those of derivatives of cellulose.

By this invention dyeings which are the equivalent of or better than those heretofore obtained may be accomplished at greatly reduced temperatures of the bath. Thus, dye baths normally requiring temperatures around the boiling point may, when the dye is treated according to this invention, be reduced to temperature around 40 C. and at the same time the time of treatment is reduced to one eighth of the time heretofore required. The colors imparted to the yarn and fabric by this shorter time and lower temperature treatment are as fast to light and scouring as the colors imparted by the prior methods.

By this invention no agitation of the dye bath either in forming the bath or while dyeing is re- A quired. Dyes treated according to this invention form smooth and uniform emulsions in cold or hot aqueous baths by merely pouring the dye dis solved in the carrier into the bath. These emulsions are stable for long periods of time and do not settle out or form into strata upon standing.

Consequently no agitation is required to maintain.. a uniform emulsion and even distribution of the dye.

In accordance with this invention, I impart color to yarns, films and fabrics with water insoluble dyestufis and the sulphonated dyestuffs which are similar thereto, by dissolving the dye in V a sulphonated naphthene or its equivalent, that is any sulphonated oil that is a solvent for the dyestuff, and an oil prior to forming a bath or printing paste therewith.

This invention is applicable to yarns or the like containing organic derivativesof cellulose. Under the term yarns are included, threads, assembli'es or bundles of a number of continuous filaments which may be in parallel relationship or which may be twisted together, artificial bristles, straws, short lengths of staple fibres, or yarn spun from such staple fibres.

The yarns to be treated may contain, besides cellulose derivatives, efi'ect materials such as pigments or filling materials, dyes or lakes, fire retardants, plasticizers, sizes and lubricants. Ex-

amples of pigments and filling materials are finely divided or powdered metals, metal oxides and salts, lamp black, logwood dye and organic substances which are translucent to light when in-' corporated with the yarns. Any of the various types of yarn may be coated with lubricants, such as light mineral oil, wool fat-oils, olive oil and like lubricants.

This invention is applicable to processed yarn I such as yarn that has been formed into hanks,

cheeses, cops, cards, etc. and yarns that have been formed into fabrics by weaving; warp knitting, circular knitting, netting, knotting, braiding or other methods of forming fabrics.

The dyes that may be employed are those that are insoluble or only slightly soluble in water and that have an afflnity for the material to be dyed. Thus, in dyeing cellulose derivatives, any insoluble or diflicultly soluble coloring matter or organic compound having an afiinity for the cellulose ester or ether material under treatment or capable of coloring the same may be utilized for the purpose of the present process in dyeing cellulose derivatives. In the case of dyeing by the azoic or development process, either the base or the developer or both may be applied according to this invention by the aid of the new dispersing and carrying agents. As instances of suitable bodies or materials may be mentioned the coloring matters or arganic compounds or classes of coloring matters or compounds referred to in U. S. Patents Nos. 1,618,413, 1,545,819, 1,600,277, 1,641,965, 1,618,415, 1,694,414 and 1,679,935, U. S. application S. No. 591,235 filed Feb. 5, 1932, British Patents Nos. 239,470 and 283,081, the coloring matters-of U. S. application S. No. 287,646 filed June 22, 1928, containing one or more keto-acidyl groups and particularly acetoacetyl groups, the

nitro-diarylamines specified in U. S. applization S. No. 311,252 filed Oct. 8, 1928, the unsulphonated thiazole derivatives of U. S. Patent 1,871,673, the azo dyes containing the xanthene or thioxanthene nucleus ofU. S. application S. No. 323,211 filed Dec. 1, 1928 and the azo dyes of U. S. application S. No. 297,098 filed Aug. 2, 1928 containing the anthraquinone nucleus.

Any of the above coloring materials or mixtures of the same or their equivalents and similar substances are dissolved in sulphonated naphthenic bodies or sulphonated oily materials that are solvents for the coloring materials. The dyes or coloring materials may be first ground and then mixed with the sulphonated bodies or they may be ground in the presence of the sulphonated bodies which act, by their solvent action, to prevent recrystallization or regrouping of particles of the organic dyestuif bodies. The amount of coloring materials will be slightly less than previously used and the quantity of sulphonated bodies will depend somewhat on whether the coloring materials are to be applied to the yarn or fabric from a bath or printing paste, on whether the yarn has a coating of oil thereon, in which case a slight excess of the sulphonated body is used, and on the type of material to be dyed. Examples of the sulphonated bodies that may be used according to this invention are sulphonated naphthenes,

sulphonated naphthenic acids, sulphonated mineral oils or fractions and residues of such obtained in their distillation, sulphonated mineral oils that have been sulphonated in the presence of fatty oils and/or their acids such as olein, stearin and other such glycerides.

phase of the emulsion.

All the dyestufi or coloring material need not be dissolved or wetted by the sulphonated body as the sulphonated body may be saturated with dyestuff and further dyestuff added which will be held in a dispersed condition by the presence of the saturated sulphonated bodies. Where there is an excess of dyestufl in relation to the sulphonated body the dye bath may nevertheless be exhausted as the sulphonated body first gives up its dissolved dye to the yarn or fabric and then takes up the dispersed dyestufi in the bath and in turn gives this up to the yarn and fabric, retaining in the end none of the dyestufi. The dyestufi apparently has a far greater amnity for the yarn than for the sulphonated body.'

These dyestuiis admixed with sulphonated bodies are especially adaptable for dyeing from aqueous baths. These aqueous baths may contain protecting salts, such as the inorganic salts, acid, alkali or ammonia for maintaining the bath at a desired pH concentration, soap or other scouring materials, oils and sizes.

These dyestuffs admixed with sulphonated bodies, in which at least a part of the dyestuff is dissolved, may be applied to fabrics from printing pastes by means of engraved or otherwise surfaced rollers or by spraying, brushing or padding of stencils which are suitably positioned over the fabric or yarn. These printing pastes and concentrated solutions may contain volatile solvents, lubricants such as oils, carriers and soaps such as the glycols, glycerols and their ethers and esters, the glycol and glycerol oleates, stearates, etc., and the alkylolamine salts of the fatty acids.

For acting as a carrier in both aqueousbaths and printing pastes, the sulphonated naphthenic bodies are preferably mixed with or dissolved in varying proportions, from equal proportions to 20/80 parts in either order, of an oil suchas light mineral oil, olive oil and the like. In dyeing from an equeous bath, no oil need be used unless it is desired to impart a finish to the material. The sulphonated bodies may be mixed with or dissolved in the oil prior or subsequent to the mixing in and dissolving of the dyestufi or coloring matter therein. These solutions or mixtures form uniform stable emulsions in the cold or hotaqueous bath by mere pouring of same into the bath.

As a guide to the proportions of ingredients to be used and other factors of dyeing, the following examples are given.

Example I There is dissolved 8 parts of 1-hydroxy-4-amino-anthraquinone in 92 parts of a sulphonated naphthene having a total sulphur, as $04, content of 1.05%. However, the S04 content of the sulphonated naphthene may be from 3 to 4%. To this solution there is added suflicient triethanolamine to bring the pH value of the bath to 7.8. This solution is poured into an aqueous bath having a weight of 30 times the weight of the yarn to be dyed. The ratio of the weight of the dyestuif to the yarn is 0.4 of dyestuif to of yarn. Cellulose acetate yarn in hank form is worked in the bath for 2 minutes at a temperature of 65 C. The dye is more than 99% exhausted from the bath and the yarn is dyed red uniformly and is fast to light and scouring.

Example II Example I is repeated using as the dyestufi 4- nitrobenzene- 1-azo-4-amino-3 6 dimethyl-benzene. A finely dispersed stable emulsion is obtained accompanied by the same quick uniform dyeing as obtained in Example I, the material being dyed orange.

Example Ill Example I is repeated using as the dyestufl a mixture of l:hydroxy 4zmonomethylainino anthraquinone and symmetrical dimethyl 1:4 diamino anthraquinone. Substantially the same improved results are obtained as in Examples I and II, the material being dyed blue.

Example IV Substantially the same dye bath is prepared as in Example I except that the temperature thereof is lowered to 40 C. The dye is exhausted from the bath within 5 to 10 minutes. The dyeing is rapid and uniform, and the color imparted is 10 fast to light and scouring.

Example V Substantially the same dye bath is prepared as in Example I except that a slightly larger 5 amount of 4-amino-benzeneazo-e-naphthyiamine is used as the dyestuff. This dyestuff is a dye base of a diazotizable and deveiopable dye. The dye base is exhausted from the bath in about 2 minutes and the sulphonated bodies do not have 20 any harmful eifect or uneconomical eifect on the subsequent diazotization and development of the dye base. The dye base may be coupled with alpha hydroxy naphthoic acid in a normal manner imparting to the yarn a uniform deep black. 25 After dyeing with the dye base, the material is preferably rinsed and diazotized in a separate bath otherwise the acid will tend to throw down the sulphonated naphthene and produce patchy results. 30

Example VI Example I is repeated except that 3 parts of dyestufi are used to 7 parts of the sulphonated bodies. In such a ratio, although all of the dyestufi is not in solution in the sulphonated body, the dyestufi is exhausted from the dye bath in about 3 minutes.

Many modifications of the above described processmay be employed without departing from the spirit of the invention. For example, this invention may be employed in conjunction with expedients heretofore employed in dyeing, such as employing levelling agents in the dye bath. There may also be employed retardants for lengthening the time of the materials in the dye bath where the present invention makes the dyeing too rapid at the temperatures which may be necessary to dye materials of mixed yarns, some of which require dyes not coming within the above types but which had been added to the same dye bath.

Having described my invention, what I desire to secure by Letters Patent is:

1. The method of improving organic derivative of ce lulose materials by incorporating therein a 55 water-insoluble organic substance having an aflinity for organic derivatives of cellulose, which comprises applying to said materials an aqueous emulsion comprising a sulphonated naphthene and an unsulphonated naphthene, the particles 60 ,of which unsulphonated naphthene have the substances dissolved coloring matter, having an afiinity for organic derivatives of cellulose, from an aqueous emulsion comprising a sulphonated mineral oil as the emulsifying agent and an unsulphonated oil, the

particles of the unsulphonated oil having the water-insoluble coloring matter dissolved therein.

4. The method of producing colorations on cellulose acetate material, which comprises applying to said material, at temperatures below 65 C. a water-insoluble coloring matter, having an ailinity for cellulose acetate, from an aqueous emulsion comprising a sulphonated naphthene as the emulsifying agent and an unsulphonated oil, the particles of the -unsulphonated oil having the water-insoluble coloring matter dissolved therein.

5. The method of producing colorations on cellulose acetate material, which comprises applying to said material a water-insoluble coloring matter, having an affinity for cellulose acetate, from an aqueous emulsion comprising a sulphonated naphthene as the emulsifying agent and an unsulphonatecl mineral oil, the particles of the unsulphonated mineral oil having the-water-insoluble coloring matter dissolved therein, the treatment of the cellulose acetate material being carried out for 2 to 10 minutes at a temperature of 40 to 65 C.

6. The method of producing colorations on organic derivative of cellulose material, which comprises applying to said material a water-insoluble coloring matter, having an aifinity for organic derivatives of cellulose, from an aqueous emulsion comprising a sulphonated naphthene and an unsulphonated naphthene, the particles of the unsulphonated naphthene having the water-insoluble coloring matter dissolved therein.

' '7. I'he method of producing colorations on cellulose acetate material, which comprises applying to said material a water-insoluble coloring matter, having an aflinity for cellulose acetate, from an aqueous emulsion comprising a sulphonated naphthene and an unsulphonat'ed naphthene, the particles of the unsulphonated'naph- 

